CN111205905A - Polyphenol antioxidant for ester lubricating oil and preparation method thereof - Google Patents
Polyphenol antioxidant for ester lubricating oil and preparation method thereof Download PDFInfo
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- CN111205905A CN111205905A CN202010077645.0A CN202010077645A CN111205905A CN 111205905 A CN111205905 A CN 111205905A CN 202010077645 A CN202010077645 A CN 202010077645A CN 111205905 A CN111205905 A CN 111205905A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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Abstract
The invention discloses a polyphenol antioxidant for ester lubricating oil and a preparation method thereof. The polyphenol antioxidant is tris (3, 5-dialkyl-4-hydroxyphenyl) -alkyl acid phloroglucinol ester antioxidant, the preparation condition is mild, and the tris (3, 5-dialkyl-4-hydroxyphenyl) -alkyl acid phloroglucinol ester with high yield can be prepared under mild condition by taking phloroglucinol and 3, 5-dialkyl-4-hydroxyphenyl-alkyl acyl chloride as raw materials, using a mixed solvent of dichloromethane and pyridine and triethylamine as a catalyst. The phenolic ester antioxidant formed by taking phloroglucinol as a bridging structure has excellent thermal stability, and meanwhile, the phenolic ester structure has good solubility in polar ester base oil, so that the antioxidant performance of the ester lubricating oil can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lubricating oil additives, relates to an antioxidant for improving the quality of lubricating oil, and particularly relates to a polyphenol antioxidant for ester lubricating oil and a preparation method thereof.
Background
The antioxidant property of the lubricating oil is one of the key factors influencing the service life of the lubricating oil and mainly depends on the oxidation stability of the lubricating base oil and the antioxidant effect of the antioxidant. The ester base oil as an important fifth type lubricating base oil has good oxidation stability, lubricating performance, viscosity-temperature performance and low-temperature flow performance, and has good solubility for additives due to the ester polar group contained in the molecular structure of the ester base oil.
In patent CN 101805145B, concentrated sulfuric acid is used as a catalyst, mesitylene and 3, 5-dialkyl-4-hydroxybenzyl methyl ether are reacted to prepare a multi-hindered phenol antioxidant, and the structural formula is as follows:
the preparation method has large amount of waste acid, and is not beneficial to large-scale industrial production. In addition, the benzene rings in the structure are only connected through methylene, so that the solubility of the antioxidant in ester lubricating oil is difficult to ensure by a short carbon chain structure between the benzene rings.
Patent CN 107245040B uses p-phenylenediamine as a bridging structure to prepare a bisphenol antioxidant containing an amide structure, and the structure is as follows:
patent CN 102432870B also discloses a polyphenol antioxidant containing an amide structure, which has poor solubility in an ester oil system due to the amide group belonging to a strong polar functional group.
Lei Ling et al (optimization of transesterification reaction conditions in the production of pentaerythritol tetrakis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], chemical industry and engineering technology, 2003, 24(6):18-20) reported a preparation process of a polyphenol type antioxidant, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] antioxidant, but the thermal stability of the polyphenol type antioxidant is limited to a certain extent by taking pentaerythritol as a bridging structure.
Disclosure of Invention
The invention aims to provide a polyphenol antioxidant for ester lubricating oil and a preparation method thereof, and solves the problems of poor antioxidant effect and poor compatibility of the antioxidant in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyphenol antioxidant for ester lubricating oil is characterized by having the following chemical formula:
wherein R1 is a steric hindrance group and R2 is an alkyl carbon chain.
Preferably, the R1 is an alkyl steric hindrance group.
Preferably, R1 is any one of propyl, butyl, pentyl and hexyl.
Preferably, R1 is an isopropyl group, a tert-butyl group, an n-pentyl group or a neopentyl group with symmetrical space structure.
Preferably, the R2 position C-C alkyl carbon chain.
A polyphenol antioxidant for ester lubricating oil is characterized in that: is prepared from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and phloroglucinol through esterification reaction.
A polyphenol antioxidant for ester lubricating oil is characterized in that: the polyphenol antioxidant for the ester lubricating oil is tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester or bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] p-phenylenediamine ester.
A preparation method of a polyphenol antioxidant for ester lubricating oil is characterized by comprising the following steps:
step 1, dissolving phloroglucinol or hydroquinone in a mixed solvent of dichloromethane and pyridine, and then adding triethylamine to obtain a solution A;
and 3, controlling the temperature of the solution A obtained in the step 1 to be normal temperature, dropwise adding the solution B obtained in the step 2 into the solution A obtained in the step 1, controlling the dropwise adding time and the reaction time, and separating a reaction product after the reaction is finished to obtain the tri [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester or the di [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] p-phenylphenol ester.
Further, the molar ratio of the phloroglucinol to the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1: 3-1: 5;
the molar ratio of hydroquinone to 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1: 2-1: 4;
the molar ratio of the phloroglucinol or hydroquinone to the triethylamine is 1: 4-1: 8;
the volume ratio of the dichloromethane and pyridine mixed solvent is 8: 1-16: 1.
Further, the temperature of the solution A in the step 1 and the step 3 is maintained at 20-40 ℃, the dropping time of the solution B in the step 3 is 0.5-1.5 h, and after the dropping is finished, the continuous reaction time is controlled to be 1-2 h.
Further, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is prepared by adopting methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the specific method is as follows:
step 1, reacting methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate with alkali liquor to prepare 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid;
and 2, reacting the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with thionyl chloride in an inert gas atmosphere to obtain the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride.
The invention has the beneficial effects that:
the invention adopts mixed solvent of dichloromethane and pyridine, uses phloroglucinol and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride as raw materials to prepare the polyphenol antioxidant tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester for ester lubricating oil, and has mild preparation conditions and high yield. The phenolic ester antioxidant formed by taking phloroglucinol as a bridging structure has excellent thermal stability, and in addition, in the structure of the antioxidant, benzene rings are connected with each other by alkyl chains and ester structures, so that the solubility of the antioxidant in polar ester oil can be ensured, and the antioxidant performance of the ester lubricating oil can be effectively improved.
Drawings
FIG. 1 is a scheme for the preparation of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in an example of the present invention;
FIG. 2 is an infrared spectrum of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in example of the present invention;
FIG. 3 is a structural formula of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] phloroglucinol ester in an embodiment of the present invention;
FIG. 4 is an infrared spectrum of phloroglucinol tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in example of the present invention;
FIG. 5 is a first-order mass spectrum of phloroglucinol tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in an example of the present invention;
FIG. 6 is a secondary mass spectrum of phloroglucinol tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in an example of the present invention;
FIG. 7 is a three-level mass spectrum of phloroglucinol tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in the example of the present invention;
FIG. 8 is a thermogravimetric plot of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] phloroglucinol ester;
FIG. 9 is a graph of the heat flow of a diisooctyl adipate oil sample with 1.0 wt% antioxidant.
Detailed Description
The invention provides a polyphenol antioxidant for ester lubricating oil, which has the following structural formula:
wherein R1 is a steric hindrance group, and is specifically any one of propyl, butyl, pentyl and hexyl. More preferably, it may be an isopropyl group, a tert-butyl group, an n-pentyl group or a neopentyl group which is sterically symmetrical. The invention utilizes the hydroxyl of phenol and the steric hindrance group at the ortho position to achieve the effect of improving the antioxidant capacity, and particularly, when the steric hindrance group is of a symmetrical structure, the antioxidant capacity is the best. R2 is an alkyl carbon chain, R2 is preferably not too long, nor too short, and is generally a 2-carbon chain, and if too long, the structure of the polyphenol antioxidant is not symmetrical, but R2 has at least two carbons for the convenience of reaction. The synthesis process of the present invention is illustrated below by R1 being t-butyl and R2 being two carbon chains, and it should be noted that when R1 and R2 are other groups, the synthesis route and process are similar, and the preparation process is easy for those skilled in the art to prepare according to the reaction conditions and procedures of the present invention.
The synthesis mode of the invention can adopt two process routes, the first method is to adopt esterification condensation reaction to directly prepare, for example, the tri [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester is obtained by esterification reaction of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and phloroglucinol, but the direct esterification reaction has low efficiency and poor economic benefit, so the invention also provides a low-cost synthesis path which is convenient for industrial industrialization. The method comprises the following specific steps:
step 1, dissolving phloroglucinol or hydroquinone in a mixed solvent of dichloromethane and pyridine, and then adding triethylamine to obtain a solution A;
and 3, controlling the temperature of the solution A obtained in the step 1 to be normal temperature, dropwise adding the solution B obtained in the step 2 into the solution A obtained in the step 1, controlling the dropwise adding time and the reaction time, and separating a reaction product after the reaction is finished to obtain the tri [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester or the di [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] p-phenylphenol ester.
The process route adopts a self-made raw material 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, the preparation route is shown in figure 1, and the following specific cases are given:
dissolving 11.70g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in 20mL of methanol, adding 8mL of NaOH solution with the concentration of 0.3g/mL, heating to 65 ℃, reacting for 4 hours, cooling to room temperature, dropwise adding 12.3% hydrochloric acid solution under the stirring condition, and adjusting the pH value of the reaction solution to 1-3. A large amount of insoluble substances are separated out, filtered and washed to be neutral by water, and a filter cake is collected and dried to obtain the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid. Thin-layer chromatography detection shows that the methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is completely converted into 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid.
Step (2) 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (5.57g) was dissolved in 70mL of toluene, 5.71g of thionyl chloride was added dropwise, the reaction solution was heated to 100 ℃ under a nitrogen atmosphere, refluxed for 2 hours, and then cooled. The toluene solvent and excess thionyl chloride were removed by distillation under reduced pressure to give 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride as a yellow solid.
The infrared spectra of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride are shown in FIG. 2. The stretching vibration peak of the ester carbonyl of the methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was 1719cm-1The carbonyl stretching vibration peak of the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid is at 1706cm-1，3300～2500cm-1The broad peak of (A) is the hydroxyl association peak of carboxylic acid, and the infrared spectrograms of the two substances show that the methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is hydrolyzed and converted into the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid. Compared with 3- (3)The infrared spectrogram of 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the infrared spectrogram of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride do not have 3300-2500 cm-1And the wave number of the absorption peak of the carbonyl group is 1800cm-1This peak was assigned to the carbonyl stretching vibrational peak of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, and the difference in the infrared spectra between them indicates that 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid was converted into 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride.
Example 1:
FIG. 3 is a structural formula of the polyphenol antioxidant tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] phloroglucinol ester of the present example. In a three-necked flask, 0.19g of phloroglucinol (1.5mmol) was dissolved in a mixed solvent of 5mL of methylene chloride and 0.5mL of pyridine, and 0.68g of triethylamine (6.75mmol) was further added. Dissolving 1.60g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride (5.4mmol) in 6mL of dichloromethane, dropwise adding the dichloromethane into the three-neck flask by using a constant-pressure separating funnel, controlling the temperature of a reaction system to be 20 ℃, dropwise adding the reaction system for 1h, continuing to react for 2h after dropwise adding, adding 15mL of water for quenching, separating, distilling to remove the solvent, eluting a crude product by column chromatography, wherein the eluent is a petroleum ether/ethyl acetate solvent with the volume ratio of 4:1 to obtain 1.19g of a light yellow target product, namely tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester, and the yield is 87.4%.
FIG. 4 is tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid]Infrared spectrogram of phloroglucinol ester, 1767cm-1The infrared peak of (a) is attributed to the stretching vibration peak of the carbonyl group thereof. FIGS. 5 to 7 are each tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid]Primary mass spectrum, secondary mass spectrum and tertiary mass spectrum of phloroglucinol ester. The peak having a mass-to-charge ratio m/z of 930 is tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid][ M + Na ] of phloroglucinol ester antioxidant parent ion]+The peak with mass-to-charge ratio M/z of 669 is [ M + Na ] of the antioxidant]+The secondary mass spectrum peak with the mass-to-charge ratio M/z of 409 is the [ M + Na ] of the antioxidant]+Tertiary mass spectral peaks.
FIG. 8 is a thermogravimetric curve of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] phloroglucinol ester under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min. As can be seen from the figure, the thermal decomposition temperature of the tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester is 350 ℃, which is greatly higher than that of the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester, and the thermal stability is excellent.
1.0 wt% of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester antioxidant or 1.0 wt% of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate antioxidant is added into diisooctyl adipate base oil. The oxidation induction time of the oil sample is tested by using a high-pressure differential scanning calorimetry, the oxygen pressure is 3.5MPa, the flow is 100mL/min, and the temperature is 200 ℃. Under the conditions of 200 ℃ and 3.5MPa, the diisooctyl adipate base oil can be rapidly oxidized, and the oxidation induction period is 0. FIG. 9 is a heat flow diagram of an oil sample of diisooctyl adipate with 1.0% of antioxidant, showing that the oxidation induction time of the oil sample with 1.0% of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was 6.9min and the oxidation induction time of the oil sample with 1.0% by weight of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] phloroglucinol ester oil was 16.3 min. The oxidation induction time of the tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester is 2.4 times of that of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the oxidation resistance of the ester oil can be greatly improved.
Example 2:
in a three-necked flask, 0.19g of phloroglucinol (1.5mmol) was dissolved in a mixed solvent of 6mL of methylene chloride and 0.4mL of pyridine, and 0.91g of triethylamine (9.0mmol) was further added. Dissolving 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride (6.75mmol) in 8mL of dichloromethane, dropwise adding the dichloromethane into the three-neck flask by using a constant-pressure separating funnel, controlling the temperature of a reaction system to be 30 ℃, dropwise adding for 1.5h, continuing to react for 1h after dropwise adding, adding 15mL of water for quenching, separating, distilling to remove the solvent, eluting a crude product by column chromatography, and obtaining a light yellow target product, namely 1.33g of tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester, wherein the volume ratio of the eluent is 4:1 petroleum ether/ethyl acetate solvent, and the yield is 97.7%.
Claims (12)
1. A polyphenol antioxidant for ester lubricating oil is characterized by having the following chemical formula:
wherein R1 is a steric hindrance group and R2 is an alkyl carbon chain.
2. The polyphenol antioxidant for ester-based lubricating oils according to claim 1, characterized in that: the R1 is an alkyl steric hindrance group.
3. The polyphenol antioxidant for ester-based lubricating oils according to claim 2, characterized in that: and R1 is any one of propyl, butyl, pentyl and hexyl.
4. The polyphenol antioxidant for ester-based lubricating oils according to claim 3, characterized in that: and R1 is isopropyl, tert-butyl, n-amyl alkyl or neopentyl alkyl with symmetrical space structure.
5. The polyphenol antioxidant for ester lubricating oils as claimed in any one of claims 1 to 4, wherein: the R2 position C-C alkyl carbon chain.
6. A polyphenol antioxidant for ester lubricating oil is characterized in that: is prepared from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and phloroglucinol through esterification reaction.
7. A polyphenol antioxidant for ester lubricating oil is characterized in that: the polyphenol antioxidant for the ester lubricating oil is tris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester or bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] p-phenylenediamine ester.
8. A method for preparing the polyphenol antioxidant for the ester lubricating oil as claimed in claim 7 is characterized by comprising the following steps:
step 1, dissolving phloroglucinol or hydroquinone in a mixed solvent of dichloromethane and pyridine, and then adding triethylamine to obtain a solution A;
step 2, dissolving 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in dichloromethane to obtain a solution B;
and 3, controlling the temperature of the solution A obtained in the step 1 to be normal temperature, dropwise adding the solution B obtained in the step 2 into the solution A obtained in the step 1, controlling the dropwise adding time and the reaction time, and separating a reaction product after the reaction is finished to obtain the tri [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] phloroglucinol ester or the di [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] p-phenylphenol ester.
9. The method of preparing the polyphenol antioxidant for ester lubricating oil according to claim 8, wherein: the molar ratio of the phloroglucinol to the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1: 3-1: 5;
the molar ratio of hydroquinone to 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1: 2-1: 4;
the molar ratio of the phloroglucinol or hydroquinone to the triethylamine is 1: 4-1: 8;
the volume ratio of the dichloromethane and pyridine mixed solvent is 8: 1-16: 1.
10. The method of preparing the polyphenol antioxidant for ester lubricating oil according to claim 8, wherein: the temperature of the solution A in the step 1 and the step 3 is maintained at 20-40 ℃, the dropping time of the solution B in the step 3 is 0.5-1.5 h, and after the dropping is finished, the time for continuing the reaction is controlled to be 1-2 h.
11. The method of preparing the polyphenol antioxidant for ester lubricating oil according to claim 8, wherein: the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is prepared from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate by the following specific method:
step 1, reacting methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate with alkali liquor to prepare 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid;
and 2, reacting the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with thionyl chloride in an inert gas atmosphere to obtain the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride.
12. The method of preparing the polyphenol antioxidant for ester-based lubricating oils according to claim 11, wherein: in the step 1, the preparation of the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid comprises the following steps:
dissolving 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate in methanol, adding a NaOH solution, heating to 60-70 ℃, reacting for 3-5h, cooling to room temperature, dropwise adding a hydrochloric acid solution under the stirring condition, adjusting the pH value of the reaction solution to 1-3, separating out a large amount of insoluble substances, filtering and washing to be neutral, collecting a filter cake, and drying to obtain the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113293048A (en) * | 2021-03-01 | 2021-08-24 | 安徽联亚新材料有限公司 | High-oxidation-resistance wear-resistant lubricating oil and preparation process thereof |
| WO2023098670A1 (en) * | 2021-11-30 | 2023-06-08 | 天集化工助剂（沧州）有限公司 | Polyphenol antioxidant and preparation method therefor and application thereof |
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| WO2023098670A1 (en) * | 2021-11-30 | 2023-06-08 | 天集化工助剂（沧州）有限公司 | Polyphenol antioxidant and preparation method therefor and application thereof |
| CN116463159A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Antioxidant additive, preparation method and application thereof |
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| CN111205905B (en) | 2022-04-15 |
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